Anthraquinonyl selenoethers



Patented Apr. 30, 1935 1 ,999,998

UNITED STATES PATENT OFFICE AN THRAQUIN ONYL SELENOE THERS Melvin A. Perkins, Milwaukee, Wis., assignor to E. I. 'du Pont de Nemonrs & Company, Wil-c mington, Del., a corporation of Delaware No Drawing. Application'December 20, 1933, Serial N0. 703,249 1 6 Claims. (01. zeo ssy This invention relates to the preparation of Example 1. Prepardtion of an unsubstituted, selenoethers of the -anthraquinone series and symmetrical anthraquinone selenoether more particularly to the preparation of new unsubstituted, monoor iii-substituted 1,1'- or 1, parts of 111 dlanthraqumonyl dlselemde 5 2'-anthraquinonyl-selenoethers-and to a new (prepared, for example by air oxidation offthe 5 duct of sodium selenide and l-chloroprocess for producingselenoethers generally. reactmn Q 0 In my copending UnS. patent application Ser. anthraqmnone) parts of 10 characterized by two anthraquinone nuc ei, subparts of anhydrous Sodium acetate and Parts 10 to this method of formation must necessarily The dark orange residue is Wa h solvent 15 wider in application-than the process heretofore drosulphlte but practlcany no ammty 20 described. It is a further object of this invenfor i fi It g1Ve s a Wi fi f f mm to produce and useful Lluanthrw colorationin sulphuri acid (or1g1nal d1selen1de quinonyl-selenoethers and 1,2'-selenoethers in glves an Orange coloratlon) m qmckly turns which the anthraqumone nuclei may be unsubto yellow" stit'dted or may contain the same or different Example 2.Preparation of a symmetrically 25 substituents.

substituted anthraquinone selenoether According to the present invention, anthraquinone selenols, diselenides or alkali-metal part of ,2di methy1-1,1'-anthraquinonyl selenolates are condensed with halogen-anthradiselenide bta e m -chlo m thyl quingne compounds by heating them together in anthraquinone by treatment with alkali selenicle, 30

sense of an acid binding agent and a catalyst, rather "unstable alkali selenolate which is The selenoether is obtained directly by filtering formed); 5.1 parts of 1-chloro-2-methyl-anthra- 0i? and freeing of solvent and inorganic salts by qliihone, 2 p s of d u a etat n ydr u 40 further substituted or contain similar substitu the miXtllle d, and h brown so d p duct 40 ents in corresponding positions respectively in is a d n th usua ma Th dry pr duct the anthraquinone nuclei. The unsymmetrical gives a. r se n l at n n su phuri a id selenoethers are produced when the two reacting and Gontains Selenium 'Y Se1en0- compounds are not similarly substituted or when e he1-Se= 15.2%)

Q 45 iig gg g g g i i gig 5 2 53 32 Example 3. Preparation of an unsymmetrically anthraqumone nucleL ZZZg-SllbStltllt'd CC, ,3 -0mthraqumone seleno- In carrying out this reaction, the use of approximately molecular proportions of the two 6 parts of Z-anthraquinone selenol (obtainable reactants is preferred, although an excess of by acidification of the react1on product of potas- 50 either is not detrimental. e sium selenide and 2-bromo-anthraquinone), Without any intention of being limited there- 7.5 parts of 1-oh1oroA-benzoylamino-anthraby, the following specific examples are given to quinone, 3.0 parts of anhydrous sodium acetate,

55 more fully illustrate the principles of my invenand 0.1 parts of copper powder are mixed and 55 tion. The parts used are by weight. introduced into parts of molten na hthalene.

The mixture is further heated to reflux for at least five hours, cooled slightly, diluted with solvent naphtha and filtered while still warm. The dark red solid is isolated as usual. It may be purified, for example, by vatting, filtration, and aeration of the deep red vat. There is thus obtained a fairly bright red solid which dissolves in concentrated sulphuric acid with a brown color and dyes cotton from a dark red vat a very yellowish-red shade of good strength.

Example 4.--Preparation of an unsymmetrical e, ,s'-selenoether 6.0 parts of 1,1-diamino-6,6-dianthrax1uinonyl-diselenide (prepared, for example, by air oxidation of the reaction product of l-amino-G- chloro-anthraquinone and sodium selenide) and 5.8 parts of into 80 parts of molten naphthalene containing 2 parts of anhydrous sodium acetate, and the mixture refluxed for 15 to 20 hours. After cooling slightly, the mixture is diluted with solvent naphtha and filtered while still warm (50-60 C.'). The residue is washed in turn with solvent naphtha, alcohol, and water. A rich, red-brown solid is obtained'in :good yield. It gives an intense, bright green coloration when dissolved in sulphuric acid. It vats orange .solution from which cotton is dyed in weak yellowish-red shades.

Example 5.-Preparation of an unsymmetrical disubstituted on, B'-Selenoether 60 parts of 2,2-dimethyl-l,l-dianthraquinonyl diselenide, 7.2 parts of l-benzoylaminofi-chloroanthraquinone, 20parts of calcium hydroxide and 1 part of copper powder are introduced, with stirring, into 100 parts of tetrahydronaphthalene and the mass heated to 200-205 C. for about ten hours. At the end of this time the mass is allowed to cool, then is filtered and the residue washed successively with solvent naphtha, alcohol and hot dilute hydrochloric acid. A dark brown solid is obtained. .It yields a dark greenish-brown coloration in sulphuric acidf Its vat is brown and cotton is dyed therefrom in brownish-yellow shades.

By this invention even the diselenides are converted into valuable selenoethers, which are of value as 'vat dyestuffs and which yield dyeings of yellow, brown, or red shades from brown, redbrown or dark red vats. It furthermore provides a method for preparing unsymmetrically sub- 2-bromo-anthraquinone are stirredreadily, giving a brownstituted anthraquinonyl selenides which are difficult or impossible to obtain by other methods.

When the anthraquinonyl selenolate is used in the reaction, the addition of acid binding agents is of course not necessary since the alkali-metal present in the selenolate is sumcient to take up the halogen liberated in the reaction. With a diselenide or selenol the use of an acid binding agent is preferred. Although not an essential in carrying out this reaction a catalyst may be employed to speed up the reaction and to permit the process to be carried out at lower temperatures. Any solvent may be used which will'dissolve at least one' ofthe reactants and which will not itself enter into the reaction under the con- Solvents which have a boiling point sufficiently high to permit the use of temperatures of from 209 to 225 C. are preferred, although lower boiling solvents may be used by increasing the time of the reaction.

Either. the bromo or chloro anthraquinone compounds may be used this reaction.

In the following claims the terms a halogen anthraquinone, an anthraquinonyl selenol, an anthraquinonyl selenolate or an anthraquinonyl diselenidei are used to indicate these compounds in either the substituted or unsubstituted form.

I claim: 7

1. In the preparation of'anthraquinonyl selenoethers, the step which comprises heating a halogen-anthraquinone compound with. a compound of the group consisting of an anthraquinone selenol, an anthraquinone selenolate and an .anthraquinone diselenide. 4

2. In the preparation of anthraquinonyl selenoethers, the step which comprises heating a halogen-anthraquinone compound with a com-.

pound of the group consisting of an anthraquinone selenol, an anthraquinone selenolate and an anthraquinone diselenide in the presence of a high boiling solvent.

3. In the preparation of anthraquinonyl selenoethers, the step which comprises heating a halogen-anthraquinone compound with a compound consisting of an anthraquinone selenol, and an anthraquinone diselenide .in the presence of a high boiling solvent and an acid binding agent.

4. A di-anthraquinonyl-selenoether.

5. .An a, 18-anthraquinonyl-selenoether.

6. An a, a-anthraquinonyl-selenoether.

MELVIN A. PERKINS. 

